US8327935B2 - Methods of use of a salt solution of monovalent and divalent cations in hydraulic fracturing - Google Patents

Methods of use of a salt solution of monovalent and divalent cations in hydraulic fracturing Download PDF

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US8327935B2
US8327935B2 US12/640,562 US64056209A US8327935B2 US 8327935 B2 US8327935 B2 US 8327935B2 US 64056209 A US64056209 A US 64056209A US 8327935 B2 US8327935 B2 US 8327935B2
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fracture
fluid
solution
fracturing
brine solution
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US20110146980A1 (en
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Dick Crill
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Priority to CA2783785A priority patent/CA2783785C/fr
Priority to EP10838295.3A priority patent/EP2513420B1/fr
Priority to PCT/US2010/061048 priority patent/WO2011075653A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/60—Compositions for stimulating production by acting on the underground formation
    • C09K8/62—Compositions for forming crevices or fractures
    • C09K8/66—Compositions based on water or polar solvents
    • C09K8/68—Compositions based on water or polar solvents containing organic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/60—Compositions for stimulating production by acting on the underground formation
    • C09K8/62—Compositions for forming crevices or fractures
    • C09K8/66—Compositions based on water or polar solvents
    • C09K8/665—Compositions based on water or polar solvents containing inorganic compounds

Definitions

  • the present invention relates to production of hydrocarbons such as crude oil and natural gas from subterranean formations via wells drilled into the formation. Specifically, the invention relates to fracturing subterranean formations to stimulate production. More specifically, the invention relates to fracture fluid compositions and methods for using them.
  • fracturing fluid a fracturing fluid
  • frac fluid hydraulically injected into a wellbore penetrating the subterranean formation and is forced against the formation strata by very high pressure.
  • the formation strata or rock is forced to crack and fracture, and a proppant is placed in the fracture by movement of a viscous-fluid containing proppant into the crack in the rock.
  • the resulting fracture, with proppant in place provides improved flow of the recoverable fluid, i.e., oil, gas or water, into the wellbore.
  • Fracturing fluids customarily comprise a thickened or gelled aqueous solution which has suspended therein “proppant” particles that are substantially insoluble in the fluids of the formation. Proppant particles carried by the fracturing fluid remain in the fracture created, thus propping open the fracture when the fracturing pressure is released and the well is put into production.
  • Suitable proppant materials include sand, walnut shells, sintered bauxite, or similar materials.
  • the “propped” fracture provides a larger flow channel to the wellbore through which an increased quantity of hydrocarbons can flow, thereby increasing the production rate of a well.
  • Dispersing fracture fluids are those which include aqueous solutions of monovalent cation salts, such as potassium chloride (KCl) and sodium chloride (NaCl), ammonium chloride (NH 4 Cl) and other salts.
  • dispersing fracture fluids may include alkoxylated fatty amines and an alkoxylated quaternary ammonium salt organic sulfates, phosphates, chlorides, fluorides, citrates, acetates, tartrates, hydrogenphosphates or a mixture thereof.
  • Other examples include ammonium sulfate, sodium sulfate, magnesium sulfate, aluminum sulfate, ammonium hydrogen phosphate, sodium hydrogen phosphate, and potassium hydrogen phosphate.
  • Aggregating fracture fluids are those which include aqueous solutions of di and trivalent cation salts, including calcium chloride (CaCl 2 ), ferric chloride (FeCl 3 ), magnesium chloride (MgCl 2 ), and other salts, for example, such as di, and trivalent metal salts of carboxylic acids.
  • Exemplary salts can also include ferric oxalate, ferric ammonium citrate, barium acetate, aluminum lactate, and magnesium formate.
  • a dispersing fracture solution in the fracture zone will disperse clays and other earthen particles and allow them to be carried by the flow-back fluids out of the hydrocarbon producing fracture zone. This process increases hydrocarbon production when the pay zone is not mostly clay.
  • an aggregating fracture solution such as CaCl 2
  • CaCl 2 an aggregating fracture solution
  • the fracturing operation is intended to create fractures that extend from the wellbore into the target oil or gas formations. Injected fluids have been known to travel as far as 3,000 feet from the well. Although attempts are made to design fracturing jobs to create an optimum network of fractures in an oil or gas formation, fracture growth is often extremely complex, unpredictable and uncontrollable. Computer models are used to simulate fracture pathways, but the few experiments in which fractures have been exposed through coring or mining have shown that hydraulic fractures can behave much differently than predicted by models.
  • a single fracturing operation in a shallow gas well may use several hundreds of thousands of gallons of water.
  • Slickwater fracs which are commonly used in shale gas formations, have been known to use up to five million gallons of water to fracture on one horizontal well.
  • fresh water is used to fracture wells because it is more effective than using wastewater from other wells. If wastewater is used, the water must be heavily treated with chemicals to kill bacteria that cause corrosion, scaling and other problems. Even freshwater fracturing operations, however, contain numerous chemicals such as biocides, acids, scale inhibitors, friction reducers, surfactants and others, but the names and volumes of the chemicals used on a specific fracturing job are almost never fully disclosed. In general, it is known that many fracturing fluid chemicals are toxic to human and wildlife, and some are known to cause cancer or are endocrine disruptors.
  • the fracture fluid of the present invention provides the properties of both a dispersing fracture solution and an aggregating fracture solution.
  • the dispersing properties of the stabilizing solution are able to act as a dispersing fracture fluid in the clay and earthen materials discharged from the pay zone, in the flow-back fluids during drilling.
  • aggregating properties of the stabilizing solution also stabilizes the pay zone and allows hydrocarbons to be released. This stabilization property allows the flow of hydrocarbon through the fractures for a significantly longer time than with prior art fluids.
  • the present invention provides a method of fracturing a subterranean formation penetrated by a well bore, comprising formulating a fracturing fluid comprising a brine solution having a mixture of monovalent and divalent cations, and pumping the fracturing fluid down the wellbore at a rate and pressure sufficient to initiate or extend a fracture in the formation.
  • the method of the present invention wherein the brine solution used in the method comprises: a deliquescent mixture of salts of monovalent and divalent cations; a sufficient amount of surfactant; and water.
  • the brine fracture fluid used in the method of the present invention can also comprise one or more additives.
  • the present invention provides a method of fracturing a subterranean formation penetrated by a well bore, comprising: obtaining a first fracturing fluid comprising a brine solution having a mixture of monovalent cations; pumping the first fracturing fluid down the wellbore at a rate and pressure sufficient to initiate or extend a fracture in the formation; obtaining a second fracturing fluid comprising a brine solution having a mixture of monovalent and divalent cations; and pumping the second fracturing fluid down the wellbore at a rate and pressure sufficient to initiate or extend a fracture in the formation.
  • the present invention provides a novel method of use of an earthen stabilizing solution as a hydraulic fracture fluid suitable for use in well drilling, having the properties of both a dispersing fracture solution, and an aggregating fracture solution.
  • composition of the fracture solution useful in the methods of the present invention is based on the brine sealant salt solution disclosed in U.S. Pat. No. 7,374,371 to Crill, and incorporated by reference in its entirety, as if set forth herein.
  • the fracture formation method of the present invention begins with formulation of a fracturing fluid comprising a brine solution having a mixture of monovalent and divalent cations, and subsequently pumping the fracturing fluid down the wellbore at a rate and pressure sufficient to initiate or extend a fracture in the formation.
  • This method causes a dispersion of clay particles with mixtures of monovalent and divalent cations in a deliquescent brine solution.
  • These cations include sodium, potassium, magnesium and calcium and similar ions.
  • the deliquescent brine solution has a density greater than water, and a sufficient monovalent and divalent cation concentration to allow the clay molecules to separate into individual molecules and disperse into solution.
  • the solution of dispersed clay molecules thus formed has the beneficial property of being able to flow out of the fractures created by the fracturing process.
  • Clays generally comprise mixtures of aluminum and iron silicates. These silicates are negatively charged in solution. It is known that when positively charged monovalent ions are added to a suspension of clays, such as the addition of Na + or K + , the positive charged ions counter the negatively charged clays allowing the molecules of clay to become more water soluble and disperse into solution. The dispersed clay in concentrated brine water allows the clay molecules to separate into individual molecules.
  • composition of brine solution used for a fracture fluid of the present invention is presented in Table 1.
  • the percentages of salts are by weight with the remainder being water.
  • the carrier or fracturing fluid used in the hydraulic fracturing method of the present invention may further contain one or more conventional additives known to the well service industry such as a gelling agent, crosslinking agent, gel breaker, surfactant, biocide, surface tension reducing agent, foaming agent, defoaming agent, demulsifier, non-emulsifier, scale inhibitor, gas hydrate inhibitor, polymer specific enzyme breaker, oxidative breaker, buffer, clay stabilizer, acid, buffer, solvent or a mixture thereof and other well treatment additives known in the art.
  • additives known to the well service industry such as a gelling agent, crosslinking agent, gel breaker, surfactant, biocide, surface tension reducing agent, foaming agent, defoaming agent, demulsifier, non-emulsifier, scale inhibitor, gas hydrate inhibitor, polymer specific enzyme breaker, oxidative breaker, buffer, clay stabilizer, acid, buffer, solvent or a mixture thereof and other well treatment additives known in the art.
  • additives
  • the brine solution having a mixture of monovalent and divalent cations may also be used with a proppant.
  • the proppant, or particulates are suspended in the brine solution having a mixture of monovalent and divalent cations, and introduced into the subterranean formation at a pressure above a fracturing pressure of the subterranean formation.
  • at least a portion of the particulate material is substantially neutrally buoyant in the carrier fluid.
  • the substantially neutrally buoyant proppant or particulate is used in a sand control method for a wellbore penetrating a subterranean formation and may be introduced into the wellbore in a slurry with the brine solution having a mixture of monovalent and divalent cations.
  • this method at least a portion of the individual particles of the particulate material may be substantially neutrally buoyant in the brine solution.
  • the fracture stimulation treatment according to the present invention typically begins with a conventional pad stage to generate the fracture, followed by a sequence of stages in which a viscous carrier fluid transports proppant into the fracture as the fracture is propagated. Typically, in this sequence of stages the amount of propping agent is increased, normally stepwise.
  • the pad and carrier fluid can be, and usually are, a gelled aqueous fluid, such as the brine solution having a mixture of monovalent and divalent cations as shown in Table 1, thickened with a viscoelastic surfactant or with a water soluble or dispersible polymer such as guar, hydroxypropylguar or the like.
  • the pad and carrier fluids may contain various additives. Non-limiting examples are fluid loss additives, crosslinking agents, clay control agents, and mobility control agents such as fibers, breakers and the like, provided that the additives do not affect the stability or action of the formation-dissolving fluid.
  • silicone fluid L-530, and L-531 are functionally capable of carrying out additional wellbore functions such as those performed by a spotting fluid, packer-fluid, completion fluid, workover fluid and coring fluid.
  • the procedural techniques for pumping fracture stimulation fluids down a wellbore to fracture a subterranean formation are well known in the art.
  • the person that designs such fracturing treatments is the person of ordinary skill to whom this disclosure is directed. That person has available many useful tools to help design and implement the fracturing treatments, one of which is a computer program commonly referred to as a fracture simulation model (also known as fracture models, fracture simulators, and fracture placement models).
  • fracture simulation model also known as fracture models, fracture simulators, and fracture placement models.
  • Most, if not all, commercial service companies that provide fracturing services to the oilfield have one, or more, fracture simulation models that their treatment designers use.
  • One commercial fracture simulation model that is widely used by several service companies is known as FRACCADE software.
  • This commercial computer program is a fracture design, prediction, and treatment-monitoring program designed by Schlumberger, Ltd. All of the various fracture simulation models use information available to the treatment designer concerning the formation to be treated and the various treatment fluids (and additives) in the calculations, and the program output is a pumping schedule that is used to pump the fracture stimulation fluids into the wellbore.
  • the initial fluid pumped to create the initial fracture geometry is a brine solution having a mixture of monovalent and divalent cations, followed by a proppant-transporting carrier fluid in the later stages.
  • the proppant-transporting carrier fluid being a conventional polymer-viscosified aqueous fluid.
  • the proppant-transporting carrier can be a polymer-viscosified aqueous brine solution of the present invention.
  • Each is injected at pressures and rates sufficient to generate and propagate fractures.
  • the viscous formation dissolving fluid in the initial stage may be a brine solution as described in Table 1.
  • the viscosity of such a system depends upon such factors as the surfactant concentration, the environment (such as the pH and the nature and concentration of salts), the time, the temperature, and the presence of other components such as alcohols, co-surfactants and breakers.
  • the reactivity of such a system depends upon some of the same factors as well as on the nature and concentration of the formation-dissolving component. The nature of these dependencies are known, and thus the relative rates at which this carrier fluid loses viscosity, leakoff into the faces of the fracture and reacts with the formation are adjusted, and taking into account the flow rate necessary to maintain the needed pressure to maintain the hydraulic fracture open.
  • the brine solution of the present invention is pumped into the wellbore and so into the formation of interest at a pressure that exceeds the fracture initiation pressure of the formation. Once the required volume of brine solution has been injected into the formation, the pumps are shut down and the hydraulic fracture allowed close. Next, the hydraulic fracture has closed (BHP fallen below closure pressure) the well is produced to flow back the spent treating fluids.
  • the density of the brine fracture fluid used in the method of the present invention is typically between about 10 to about 11 pounds per gallon of solution, preferably between about 10.1 to about 10.2 pounds per gallon of solution, and most preferably about 10.18 pounds per gallon of solution.
  • the composition of the brine fracture fluid is preferably a mixture of magnesium and calcium chloride in a ratio of about 5 to 1 magnesium chloride to calcium chloride.
  • the composition also must have sufficient sodium chloride or potassium chloride to suspend the clay and disperse it in solution.
  • the brine fracture fluid must be deliquescent. That is, the composition will draw moisture out of the air continuously until it attains a liquid state. Examples of deliquescent salts are calcium chloride, magnesium chloride, potassium carbonate, trichloroacetic acid, calcium phosphate, nickel(II) chloride, potassium hydroxide, calcium nitrate, and sodium cyanide.
  • a particular composition of the brine solution used in hydraulic fracture is shown in Table 2. It is understood by those of skill in the art that the brine solution shown in Table 2 can be combined with one or more additives commonly used in the art and discussed previously.
  • the brine fracture fluid can be used in a two step process where the first step comprises using a brine fracture fluid that contains only monovalent cations such as sodium or potassium, to disperse the clay.
  • a brine fracture fluid such as the one described in Table 2, having both monovalent and divalent cations, is then added to fracture zone.
  • the fracture fluid of the second step may also include one or more additives.

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  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Organic Chemistry (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)
  • Lubricants (AREA)
US12/640,562 2009-12-17 2009-12-17 Methods of use of a salt solution of monovalent and divalent cations in hydraulic fracturing Active 2030-07-13 US8327935B2 (en)

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Application Number Priority Date Filing Date Title
US12/640,562 US8327935B2 (en) 2009-12-17 2009-12-17 Methods of use of a salt solution of monovalent and divalent cations in hydraulic fracturing
CA2783785A CA2783785C (fr) 2009-12-17 2010-12-17 Compositions de fluides de fracturation comprenant un melange de cations monovalents et divalents et procedes d'utilisation associes dans la fracturation hydraulique de formations souterraines
EP10838295.3A EP2513420B1 (fr) 2009-12-17 2010-12-17 Compositions de fluides de fracturation comprenant un mélange de cations monovalents et divalents et procédés d'utilisation associés dans la fracturation hydraulique de formations souterraines
PCT/US2010/061048 WO2011075653A1 (fr) 2009-12-17 2010-12-17 Compositions de fluides de fracturation comprenant un mélange de cations monovalents et divalents et procédés d'utilisation associés dans la fracturation hydraulique de formations souterraines

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Cited By (3)

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US20160376497A1 (en) * 2015-06-24 2016-12-29 Schlumberger Technology Corporation Enhanced viscosity of polymer solutions in high salinity brines
US10513652B2 (en) 2016-07-26 2019-12-24 Saudi Arabian Oil Company Addition of monovalent salts for improved viscosity of polymer solutions used in oil recovery applications
US11384277B2 (en) 2020-05-12 2022-07-12 Saudi Arabian Oil Company Manganese-assisted waterflooding processes for enhanced oil recovery in carbonate formations

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RU2017133921A (ru) * 2015-03-04 2019-04-04 СТЮАРТ ЭНД СТИВЕНСОН, ЭлЭлСи Системы гидравлического разрыва пласта с электрическими двигателями и способ использования
WO2017171811A1 (fr) * 2016-03-31 2017-10-05 Halliburton Energy Services, Inc. Amélioration des performances d'un agent de soutènement
CN114482970B (zh) * 2020-10-26 2024-05-28 中国石油天然气股份有限公司 一种支撑剂的泵注方法
CN114634806A (zh) * 2020-12-16 2022-06-17 中国石油化工股份有限公司 FeCl3在页岩气开采中的应用及水力压裂液和提高页岩气采收率的方法

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US20160376497A1 (en) * 2015-06-24 2016-12-29 Schlumberger Technology Corporation Enhanced viscosity of polymer solutions in high salinity brines
US10815765B2 (en) * 2015-06-24 2020-10-27 Schlumberger Technology Corporation Enhanced viscosity of polymer solutions in high salinity brines
US10513652B2 (en) 2016-07-26 2019-12-24 Saudi Arabian Oil Company Addition of monovalent salts for improved viscosity of polymer solutions used in oil recovery applications
US10894914B2 (en) 2016-07-26 2021-01-19 Saudi Arabian Oil Company Addition of monovalent salts for improved viscosity of polymer solutions used in oil recovery applications
US11124694B2 (en) 2016-07-26 2021-09-21 Saudi Arabian Oil Company Addition of monovalent salts for improved viscosity of polymer solutions used in oil recovery applications
US11384277B2 (en) 2020-05-12 2022-07-12 Saudi Arabian Oil Company Manganese-assisted waterflooding processes for enhanced oil recovery in carbonate formations

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EP2513420B1 (fr) 2019-04-24
CA2783785C (fr) 2015-11-17
WO2011075653A1 (fr) 2011-06-23
EP2513420A1 (fr) 2012-10-24
CA2783785A1 (fr) 2011-06-23
EP2513420A4 (fr) 2013-07-03
US20110146980A1 (en) 2011-06-23

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